Production of alcohols



United states Patent 3,157,705 PRODUCTHGN 0F ALCOHOLS Norman HenryPearce, Hull, England, assignor to The Distillers Company Limited,Edinburgh, Scotland, at

British company No Drawing. Filed Nov. 23, 1960, Ser. No. 71,918 laimspriority, application Great Britain Jan. 6, 1960 7 Claims. (Cl. Mil-631)The present invention relates to the production of alcohols byhydrolysing organic halides with water.

The invention is a process of producing an alcohol which comprisescontacting an aliphatic or aralkyl halide, other than a fluoride, withwater and an NzNdi-alkyl amide of a saturated carboxylic acid.

The aliphatic or aralkyl halide may be, for example, an alkyl,cycloalkyl, alkenyl or alkynyl halide. The halide may be a chloride,bromide or iodide.

The N-zNdialkyl amide of a saturated carboxylic acid may be, forexample, NzNdimethyl acetarnide; the preferred amide isNzN'dimethylformamide.

The process may be conveniently carried out by dispersing the halide inthe NzNdialkyl amide, and contacting the dispersion with water,preferably at a temperatu-re between 15 C. and the boiling point of themixture of the dispersion and water. Preferably the proportion of Waterpresent in the process, with respect to the halide, is at least thestoichiometnic proportion.

The process may be carried out at superatmospheric pressure, but it ispreferably carried out at substantially atmospheric pressure.

Hydrogen halide is produced by the process of the invention and the NzN'dialkyl amide is converted to its salt with the hydrogen halide. TheNzN'dialkyl amide may be recovered by adding a stronger base to thesalt, as the invention proceeds or at the end of the reaction. Ifdesired, the stronger base may be added to the mixture of the halide,water and NzN'd-i-alkyl amide at the beginning of the process,preferably in a proportion more than sufficient to neutralise all thehydrogen halide produce in the process.

The alcohol may be recovered by a conventional method, such asfractional distillation. The following examples further illustrate theinvention.

Example 1 10.1 parts by weight of water were added to a solution of 10.1parts by weight of n-butyl bromide in 25.5 parts by weight ofNzN'dimethyl formamide and the resulting mixture was boiled with refluxfor 4 hours.

98% of the n-butyl bromide was converted into nbutano'l, 2% remainingunchanged; the yield of n-butanol based on the halide consumed was 100%Example 2 9.9 parts by weight of water were added to a solution of 10.1parts by weight of secondary butyl bromide in 24.0 parts by Weight ofNzN'dimethyl formamide and the resulting mixture was boiled underrefluxfor 2 hours.

97% of the secondary butyl bromide was converted into secondary bntanol,3% remaining unchanged; the

3,157,705 Patented Nov. 17, 1964 yield of secondary butanol based on thehalide consumed was Example 3 10.6 parts by weight of water were addedto a solution of 11.3 parts by weight of cyclohexyl chloride in 31.7parts by weight of NzN'dimethyl formamide and the resulting mixture wasboiled under reflux for 3 hours.

92.0% of the cyclohexyl chloride was converted into cyclo-hexanol, 7.7%remaining unchanged; the yield of cyclohexanol based on the halide wasnearly 100%.

I claim:

1. A process of producing an alcohol which comprises dispersing a halideselected from the group consisting of lower alkyl and cyclohexylchlorides, bromides and iodides in an NtNdimethyl amide of a saturatedcarboxylic acid and contacting the dispersion with water selected fromthe group consisting of formic acid and acetic acid, at a temperaturebetween 15 C. and the boiling point of the reaction mixture.

2. A process as claimed in claim 1 wherein at least the stoichiometricproportion of Water is presentwith respect to the halide.

3. A process as claim in claim 1 wherein the N'zN'dimethyl amide of asaturated carboxylic acid is N1Ndimethyl formamide.

4. A process of producing an alcohol which comprises dispersing a halideselected from the group consisting of lower alkyl and cyclohexylchlorides, bromides and iodides in an N:N'dimethyl amide of a saturatedcarboxylic acid selected from the group consisting of formic acid andacetic acid and contacting the dispersion with water, at a temperaturebetween 15 C. and the boiling point of the reaction mixture, underatmospheric pressure.

5. A process of producing n-butanol which comprises, dispersing n-butylbromide in NzN'dimethyl formamide, contacting the dispersion with waterand subjecting the mixture to reflux until substantially completeconversion of the bromide to n-butanol is achieved.

6. A process of producing secondary butanol which comprises dispersingsecondary butyl bromide in NzN'dimethyl formamide, contacting thedispersion with water and subjecting the mixture to reflux untilsubstantially complete conversion of the bromide to secondary butanol isachieved.

7. A process of producing cyclohexanol which comprises dispersingcyclohexyl chloride in N:N'dimethyl formamide, contacting the dispersionwith water and subjecting the mixture to reflux until substantiallycomplete conversion of the chloride to cyclohexanol is achieved.

References Cited in the file of this patent UNITED STATES PATENTS2,072,016 Tamele et a1 Feb. 23, 1937 FOREIGN PATENTS 361,042 GermanyOct. 9, 1922 OTHER REFERENCES Fieser et al.: Organic Chemistry (2nded.), page 1950). i

1. A PROCESS OF PRODUCING AN ALCOHOL WHICH COMPRISES DISPERSING A HALIDESELECTED FROM THE GROUP CONSISTING OF LOWER ALKYL AND CYCLOHEXYLCHLORIDES, BROMIDES AND IODIDES IN AN N;N''DIMETHYL AMIDE OF A SATURATEDCARBOXYLIC ACID AND CONTACTING THE DISPERSION WITH WATER SELECTED FROMTHE GROUP CONSISTING OF FORMIC ACID AND ACETIC ACID, AT A TEMPERATUREBETWEEN 15*C. AND THE BOILING POINT OF THE REACTION MIXTURE.